JP2003321202A - Hydrogen storage/supply system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen storage/supply system which realizes a fuel cell system capable of quick response to electric power load change in a home and which is excellent in stability and efficiency at a low cost. <P>SOLUTION: Hydrogen is stored and/or supplied in the hydrogen storage/ supply system by utilizing at least either one of a hydrogenation reaction of a hydrogen storage body and a dehydrogenation reaction of a hydrogen supply body consisting of a hydrogen derivative. The system comprises a raw material storage means (a) to house the hydrogen storage body and/or the hydrogen supply body, a reaction apparatus (b) to house a metal carrying catalyst, a raw material supply means (c), a gas-liquid separating means (d), a reaction product recovering means (e) and a heating means (f) to heat the metal carrying catalyst. Furthermore, the metal carrying catalyst is such one that a catalytic metal is supported on a carrier consisting of a conductive material and the carrier can be heated by high-frequency induction heating. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrogen storage / supply system, and more particularly, to a hydrogenation reaction of a hydrogen storage body composed of an aromatic compound and a hydrogen supply system composed of a hydrogenated derivative of the aromatic compound. The present invention relates to a hydrogen storage / supply system that stores and / or supplies hydrogen by utilizing at least one of dehydrogenation reaction, and that is low in cost, excellent in stability and efficiency.

[0002]

2. Description of the Related Art In recent years, deterioration of the global environment, such as global warming, has become a problem. Hydrogen fuel is used as a clean energy source to replace fossil fuels, and hydrogen is used as a fuel cell as one of its usage forms. The system is in the spotlight. Since hydrogen can be produced by electrolysis of water, the hydrogen fuel is inexhaustible on the assumption that electrolysis of seawater or river water is performed. However, since hydrogen is a gas and a flammable substance at room temperature, it is difficult to store and transport it, and handling must be extremely careful.

When a fuel cell system for residential use is considered as a distributed power source, the form of hydrogen supply is important, but the method of supplying hydrogen as it is to each household has safety problems. However, there is a problem that it is necessary to develop an infrastructure for supply, and currently, the following method is considered as a practical supply form of hydrogen. A. A method of pressing hydrogen into a cylinder and delivering it to each household. B. A method to obtain hydrogen from city gas or propane gas, which is an existing infrastructure, by a method such as steam reforming. C. A method of obtaining hydrogen by electrolyzing water with electricity at night. D. A method of obtaining hydrogen by electrolyzing water with electric energy obtained from a solar cell or the like. E. A method of directly obtaining hydrogen from light energy and water by a photocatalytic reaction. F. A method for obtaining hydrogen using photosynthetic bacteria or anaerobic hydrogen-producing bacteria.

Among these, A. Can be easily realized as a supply system, but since hydrogen gas is handled at home, there is a problem in safety and it is considered to be of low practicality. On the other hand, B. Is practical in that the gas already supplied to the home can be used, but there is a problem that the reformer's responsivity to the load change in the home is not sufficient. In addition, C.I. ~ F. However, since there is a time lag between the supply side and the demand side, there is a problem that it is not possible to follow the load fluctuation in the home.

[0005] Therefore, the above-mentioned B. ~
F. In order to realize the method described above, a hydrogen storage / supply system that temporarily stores the generated hydrogen and supplies the hydrogen to the fuel cell system with a good response when necessary is being studied. For example, JP-A-7-192746. In the publication, a system using a hydrogen storage alloy is disclosed in Japanese Patent Laid-Open No. 5-27080.
No. 1 publication discloses fullerenes and carbon nanotubes,
A system using a carbon material such as carbon nanofiber is disclosed.

However, in a system using a hydrogen storage alloy, it is possible to construct a simple system capable of controlling the input and output of hydrogen by heat, but the hydrogen storage amount per unit weight of the alloy is low, and in the case of a typical LaNi alloy, However, the storage amount of hydrogen is only about 3% by weight. Also, since it is an alloy, it is heavy and lacks stability. further,
The high price of alloys is also a big problem in practical use.

Further, in the system using a carbon material, a material capable of highly absorbing hydrogen is being developed, but it is still insufficient. For example, carbon nanotube has a large bulk density and a storage amount per unit volume is large. The low size makes the system large. Further, these materials are difficult to synthesize on an industrial scale, and none of them has been put to practical use.

Under such circumstances, the present applicants have proposed a benzene / cyclohexane-based hydrocarbon or a naphthalene / decalin / tetralin-based hydrocarbon as a hydrogen storage / supply system that is low in cost and excellent in safety, transportability, and storage capacity. Paying attention to
Hydrogen storage that stores and / or supplies hydrogen by using at least one of a hydrogenation reaction of a hydrogen storage body composed of an aromatic compound and a dehydrogenation reaction of a hydrogen supply body composed of a hydrogenated derivative of the aromatic compound・ Developed a supply system. This hydrogen storage / supply system supplies saturated hydrocarbons such as cyclohexane and decalin to the metal-supported catalyst (supporting metal such as platinum carrying metal such as platinum on the carrier such as activated carbon) in the reactor in the form of mist. On the other hand, hydrogen is generated, and on the other hand, benzene, naphthalene and the like are similarly injected to a metal-supported catalyst in a reactor filled with hydrogen to store hydrogen (Japanese Patent Application No. 2000-388043).

In such a hydrogen storage / supply system, from the viewpoint of the stability and efficiency of the reaction, all the raw materials injected to the catalyst immediately react and are discharged from the reactor,
It is desirable that a new raw material can be supplied promptly and the reaction can continue efficiently and stably. In particular, when hydrogen is generated by a dehydrogenation reaction and is supplied to a fuel cell for power generation, the amount of power generation fluctuates when the amount of hydrogen generation fluctuates, so it is possible to supply hydrogen more stably. Is required.

However, in the above hydrogen storage / supply system, when a predetermined amount of raw material is injected, the catalyst heated to 200 to 350 ° C. is cooled by the low temperature liquid raw material, especially when hydrogen is generated. As a result, the catalyst temperature is lowered, and the endothermic reaction accompanying the dehydrogenation reaction causes the catalyst temperature to be drastically lowered, the reaction is stopped in the middle, and a part of the raw material may remain unreacted. That is, since the dehydrogenation reaction is an endothermic reaction, more heat energy is required following the reaction, but it was difficult with the conventional method. Further, although the catalyst returns to a high temperature by the heating means, most of the unreacted raw material remains in the reaction apparatus in a vaporized state without partially reacting with it. Such an unreacted residual gas may hinder the reaction due to the supply of new raw material. Further, most of the product gas generated by the reaction is discharged to the outside of the reactor due to the volume expansion due to vaporization and evaporation, but a part of the product gas stays in the reactor and the reverse reaction occurs to cause the original reaction. There was a possibility of returning to the raw material.

Therefore, it is strongly demanded to develop a hydrogen storage / supply system at low cost, which is excellent in stability and efficiency, which enables a fuel cell system capable of quickly responding to a load fluctuation of electric power in a home. It was being done.

[0012]

SUMMARY OF THE INVENTION In view of the above problems of the prior art, an object of the present invention is to enable a fuel cell system capable of quickly responding to a load fluctuation of electric power at home.
It is to provide a hydrogen storage / supply system that is low in cost and excellent in stability and efficiency. In particular, when hydrogen is generated, the catalyst heated to 200 to 350 ° C. is cooled by the low temperature liquid raw material to lower the catalyst temperature, and the endothermic reaction accompanying the dehydrogenation reaction causes the catalyst temperature to drop sharply. It is an object of the present invention to provide a hydrogen storage / supply system that can supply more heat energy following a reaction so that the reaction does not stop midway and a part of the raw material remains unreacted.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the hydrogen storage reaction of an aromatic compound and a hydrogenated derivative of the aromatic compound were carried out. In a hydrogen storage / supply system for storing and / or supplying hydrogen by utilizing at least one of dehydrogenation reaction of a hydrogen supplier, a raw material storage means, a reaction device, a raw material supply means, and a gas-liquid separation means , Constructing a system consisting of a reactant recovery means, in which case, a metal-supported catalyst to be housed in a reaction device is supported on a carrier made of a conductive material, and the conductive metal is heated by high-frequency induction heating. It was found that the above-mentioned problems can be achieved by such a constitution, and the present invention has been completed based on such findings.

That is, according to the first aspect of the present invention,
Hydrogen storage that stores and / or supplies hydrogen by using at least one of a hydrogenation reaction of a hydrogen storage body composed of an aromatic compound and a dehydrogenation reaction of a hydrogen supply body composed of a hydrogenated derivative of the aromatic compound A supply system, wherein the system stores a hydrogen storage and / or a raw material storage means (a) containing the hydrogen supply, and hydrogenates the hydrogen storage and / or dehydrogenates the hydrogen supply. Reactor (b) accommodating a metal-supported catalyst, and a hydrogen storage body in a raw material storage means and / or
Alternatively, a raw material supply means (c) for supplying a hydrogen supplier to the reactor, and a gas-liquid separation means (d) for condensing the produced gas from the reactor to separate hydrogen into a hydrogen storage body and / or a hydrogen supply body. , A reactant recovery means (e) for recovering the separated hydrogen storage body and / or hydrogen supply body, and a heating means (f) for heating the metal-supported catalyst, and the metal-supported catalyst is electrically conductive. There is provided a hydrogen storage / supply system comprising a carrier made of a material and a catalytic metal supported on the carrier, and the heating means is configured to enable high frequency induction heating of the carrier. It

According to the second aspect of the present invention, the first aspect
In the invention, the catalyst metal is at least one metal selected from the group consisting of nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron. Claim 1 characterized by the above.
A hydrogen storage / supply system described in 1. is provided.

According to a third aspect of the present invention, the first aspect
In the above invention, the carrier has a specific surface area of 1000 m ^2.
There is provided a hydrogen storage / supply system, which is a porous metal body having a metal content of at least ³ / m ³ .

According to the fourth aspect of the present invention, the third aspect
In the invention, the above-mentioned metal porous body is a porous body of nickel or an alloy thereof, that is, hydrogen storage
A supply system is provided.

Further, according to a fifth aspect of the present invention, there is provided the hydrogen storage / supply system according to the third aspect, wherein the metal porous body has a cylindrical shape.

Further, according to a sixth invention of the present invention, in the first invention, the carrier has an electric resistivity of 100Ω.
Provided is a hydrogen storage / supply system characterized by being a felt-like carbonaceous material of m or less.

Further, according to a seventh aspect of the present invention, in the first aspect, the reaction device (b) is formed of at least one tubular body, and one end of the tubular body is the raw material. There is provided a hydrogen storage / supply system characterized in that the supply means (c) and the other end communicate with the gas-liquid separation means (d).

Further, according to an eighth invention of the present invention, in the seventh invention, a coil-shaped electromagnetic induction coil for heating the metal-supported catalyst so as to surround the tubular body of the reactor (b). Is arranged, and at that time, the temperature of the metal-supported catalyst is adjusted by detecting the catalyst temperature by a thermocouple in contact with the metal-supported catalyst and adjusting the high-frequency current to the electromagnetic induction coil. A hydrogen storage / supply system is provided.

Further, according to a ninth invention of the present invention, in the seventh invention, in the cylindrical body of the reaction apparatus (b), a cylindrical metal porous body or a felt-like body having an inner diameter corresponding to the inner diameter thereof is formed. Provided is a hydrogen storage / supply system characterized by being loaded with a carbon-based material.

Further, according to the tenth invention of the present invention,
In a seventh aspect of the invention, there is provided a hydrogen storage / supply system, wherein the tubular body is formed of an insulator having heat resistance, heat insulation and non-high frequency dielectric heating.

Further, according to the eleventh invention of the present invention,
In the tenth invention, the insulator is made of at least one inorganic material selected from the group consisting of quartz glass, alumina, and ceramics.
A supply system is provided.

Further, according to the twelfth invention of the present invention,
In the first invention, the aromatic compound is benzene,
The compound is at least one compound selected from the group consisting of toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and alkyl derivatives thereof.
A hydrogen storage / supply system described in 1. is provided.

Further, according to the thirteenth invention of the present invention,
In the first invention, the hydrogenated derivative is at least one selected from cyclohexane, methylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, decahydronaphthalene (decalin), and alkyl derivatives thereof. Provided is a hydrogen storage / supply system characterized by being a compound.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

1. Basic configuration of hydrogen storage / supply system The hydrogen storage / supply system of the present invention, as described above,
(A) A raw material storage means for accommodating a hydrogen storage body and / or a hydrogen supply body, and (b) a reaction apparatus for accommodating a metal-supported catalyst for hydrogenating the hydrogen storage body and / or dehydrogenating the hydrogen supply body. And (c) a raw material supply means for supplying the hydrogen storage body and / or the hydrogen supply body in the raw material storage means to the reactor,
(D) Gas-liquid separation means for condensing the produced gas from the reactor to separate hydrogen into a hydrogen storage body and / or hydrogen supply body, and (e) recovering the separated hydrogen storage body and / or hydrogen supply body. It comprises a reactant collecting means and a heating means (f) for heating the metal-supported catalyst. Further, the metal-supported catalyst has a catalyst metal supported on a carrier made of a conductive material. Is configured to be capable of high-frequency induction heating, but it is preferable that the basic configuration includes a control means for controlling the conditions of the hydrogenation reaction and / or the dehydrogenation reaction in the reactor. .
Hereinafter, embodiments of a hydrogen storage / supply system according to the present invention will be described in detail with reference to the drawings.

(Embodiment 1) FIG. 1 is an explanatory view schematically showing an example of the configuration of a hydrogen storage / supply system capable of storing and / or supplying hydrogen. Although the configuration of FIG. 1 shows a system capable of both storage and supply of hydrogen, it is also possible to omit unnecessary means and configure only one of them. The hydrogen storage / supply system 1 mainly includes a raw material storage means 2 and a raw material delivery means 3.
1, a reactor 4, a gas separation unit 5, a reactant recovery unit 8, a generated gas discharge unit 12, and a control unit 10.

The raw material storage means 2 is formed in a tank shape,
Benzene, which is a hydrogen storage body, or cyclohexane, which is a hydrogen supply body, is stored. The raw material supply means 3 is a component for pressurizing the benzene or cyclohexane introduced from the raw material storage means 2 to supply the raw material to the reaction device 4, and comprises a compressor (pump) 31 and a solenoid valve. The valve 32 and the raw material storage means 2 are connected by piping. The valve 32 controls the supply amount and supply time of the raw material supplied to the reactor 4.

The reactor 4 is a component that causes hydrogenation reaction or dehydrogenation reaction by bringing benzene or cyclohexane into contact with the catalyst. At least one tubular body forms the reactor. Is characterized by. The reactor 4 is formed of a cylindrical body of an insulating material having high heat resistance such as quartz glass, alumina, ceramics, etc., and a porous catalyst 41 is housed inside a cylindrical body main body 42. . One end 42a of the tubular body 42 is pipe-connected to the raw material supply means 3, and the raw material from the raw material supply device 3 is uniformly dispersed on the catalyst 41 by, for example, a dispersion plate. Incidentally, the reaction device 4
Is from the viewpoint of uniform dispersion of raw materials, heating efficiency of the catalyst, etc.
It may be formed of a plurality of thin tubes.

Here, the cylindrical body 42 may have any shape as long as it can be filled with the metal-supported catalyst while maintaining the flow path, and the inner diameter may be changed to a mortar shape or a bellows shape. The shape and size can be appropriately selected according to the use condition. Further, when the catalyst is heated by a heater such as a nichrome wire, the tubular body 42 is preferably formed of a material having good thermal conductivity such as aluminum.

As the catalyst 41, in the present embodiment, a porous catalyst in which platinum is supported on a nickel porous body or a felt-like carbon material and through which raw materials and reaction products can pass is used. Although the weight of is 10g,
The weight and size are factors to be adjusted as necessary, and are not particularly limited.

The present invention is characterized in that high-frequency induction heating is used as the catalyst heating means. In the present embodiment, the catalyst 41 is heated so as to surround the tubular body 42 of the reactor 4. The coil-shaped electromagnetic induction coil 11 is arranged, and the thermocouple 4 in contact with the catalyst 41
The temperature of the catalyst 41 is adjusted by detecting the catalyst temperature by 5 and adjusting the high frequency current to the electromagnetic induction coil.

The high frequency induction heating is for induction heating a conductor with a high frequency generated by passing a high frequency current through an electromagnetic induction coil. An eddy current is generated in the conductor due to the electromagnetic induction action, and Joule heat is generated. The conductor is heated. The frequency of the high-frequency current applied to the electromagnetic induction coil is generally 350 to 450 kHz, although it depends on the impedance matching with the conductor to be heated.

As the shape of the electromagnetic induction coil, a spiral shape can be adopted in addition to a general coil shape. In the case of the coil shape, the conductor to be heated is placed in the center of the coil, and in the case of the spiral shape, the conductor is placed on the center line of the spiral,
Can be heated efficiently and with good response.

In the case of performing high frequency induction heating, the temperature control is generally required because the conductor is continuously heated when the high frequency current is continuously supplied to the electromagnetic induction coil. As a method for controlling the temperature, various kinds of feedback control are possible, in which the temperature of the conductor is measured and the high-frequency current flowing in the electromagnetic induction coil is controlled.
At 500 ° C., feedback control using a general thermocouple is sufficient. Further, in order to balance the energy input for heating and the energy required for reaction, it is also possible to obtain the amount of heat per unit time required for reaction and control the current (electric power) applied to the electromagnetic induction coil. It is possible.

In order to heat the metal-supported catalyst more efficiently and with good response, a conductor such as carbon is used as a carrier for the metal-supported catalyst, and the metal-supported catalyst is directly heated by forming it into a shape in which eddy current is generated. Preferably.
Furthermore, in order to efficiently and instantly heat only the metal-supported catalyst, the tubular body main body is formed of a highly heat-resistant insulator such as quartz glass, alumina, or ceramic. When there are a plurality of tubular bodies, each tubular body may be surrounded by an electromagnetic induction coil for heating, or a plurality of tubular bodies may be collectively surrounded by one electromagnetic induction coil for heating. You may. Note that a plurality of electromagnetic induction coils may be arranged in the longitudinal direction of the tubular body main body, and, for example, heating may be performed in order from the raw material supply side so that the catalyst temperature increases.

The temperature of the catalyst 41 is heated to about 60 to 120 ° C. when the cyclohexane is produced by the hydrogen addition reaction of benzene by the electromagnetic induction coil 11. Considering the conversion efficiency, it is preferable to heat to 95 to 105 ° C. Further, when benzene is produced by the dehydrogenation reaction of cyclohexane, it is heated to about 220 to 400 ° C. Similarly, in consideration of conversion efficiency, it is preferable to heat to 250 to 350 ° C. The reason why the catalyst temperature of the latter is set high is that the hydrogen addition reaction is an exothermic reaction and the dehydrogenation reaction is an endothermic reaction, so that the latter requires more heat energy. Further, the other end 42b of the tubular body 42 of the reaction device 4 is connected to the gas-liquid separation means 5 through a valve 6 composed of an electromagnetic valve, and the pipe between the reaction device 4 and the raw material supply means 3 is It is branched and connected to a hydrogen supply means (not shown) through a valve 7 which is an electromagnetic valve.

The valve 6 is used when introducing the product in the reactor 4 to the produced gas discharge means 11 and the gas-liquid separation means 5. In the reactor 4, when a hydrogen addition reaction occurs between hydrogen and benzene, cyclohexane is produced, and when a dehydrogenation reaction of cyclohexane occurs, benzene and hydrogen are produced, but these products are gases. ,
The gas-liquid separating means 5 is provided for completely liquefying benzene or cyclohexane sent from the reactor 4 to separate hydrogen. In addition, the valve 7
A valve for introducing / controlling the hydrogen from the hydrogen supplying means into the reactor 4, and is used when cyclohexane is produced from benzene in the hydrogen addition reaction.

The gas-liquid separating means 5 is a heat exchanger 5 for cooling with cooling water, such as a spiral thin tube or an alternating cooling pipe structure.
A vapor condensing unit 51 composed of 1a and a hydrogen separating unit 5 such as activated carbon or a hydrogen separator film for separating droplets accompanying hydrogen.
2a of the hydrogen extraction unit 52.
The vapor condensing unit 51 optimizes, for example, by adjusting the cooling water temperature (for example, 5 to 20 ° C.) in order to efficiently realize gas-liquid separation of the generated hydrogen from the aromatic compound and the hydrogenated aromatic compound. Preferably.

The hydrogen extraction section 52 is usually the vapor condensation section 51.
Although it is not necessary to separate and purify hydrogen by manipulating various factors such as the contact area, cooling water temperature, and hydrogen generation rate, it is not absolutely necessary, but higher purity (99.9% If the hydrogen supply of above) is required, it is necessary to purify hydrogen using conventional technology such as activated carbon, silica separation membrane of hydrogen separator membrane, palladium / silver separation membrane, etc. In the embodiment, it is additionally installed. A gas-liquid separation unit (not shown) filled with, for example, glass wool, wire mesh or the like is provided between the reactant recovery unit 8 and the hydrogen extraction unit 52, and the droplets are entrained in the hydrogen extraction unit 52. The amount can also be reduced.

The reactant collecting means 8 is connected to the vapor condensing section 51 of the gas-liquid separating means 5 by piping, and the cyclohexane or benzene cooled and liquefied in the vapor condensing section 51 is sent to the reactant collecting means 8. Be recovered. The reactant recovery means 8 is also connected to the hydrogen extraction part 52 of the gas-liquid separation means 5 by piping, and the generated hydrogen once enters the reactant recovery means 8 together with cyclohexane or benzene liquefied in the vapor condensing part 51. After that, the hydrogen is sent to the hydrogen extraction unit 52, and the hydrogen separation unit 52a including the activated carbon and the hydrogen separator film installed in the hydrogen extraction unit 52 separates and purifies only the hydrogen gas having a light mass and a high diffusion rate. . The purified hydrogen is efficiently supplied to the outside, for example, a residential fuel cell system or the like through a pipe 91 connected to the hydrogen extraction unit 52 and a hydrogen discharge side valve 92.

As described above, the hydrogen extraction section 52 of the gas-liquid separation means 5 is usually unnecessary, so the vapor condensation section 51 of the gas-liquid separation means 5 and the outlet of the hydrogen extraction section 52 are directly connected by piping to extract hydrogen. Alternatively, hydrogen may be sent to the pipe 91 by bypassing the portion 52, and liquid cyclohexane or benzene accumulated at the bottom of the vapor condensing portion 51 may be recovered by the reactant recovery means 8. Further, since the sensor 91 for measuring the generated gas amount is installed in the pipe 91, the generated amount of hydrogen can be measured.

On the other hand, the compressor (pump) 31, the valve 32, the heater 43, the thermocouple 45, the valve 6, the valve 7, the valve 92, and the sensor 93 respectively include the control means 10.
It is electrically connected to the thermocouple 45, and based on information from the thermocouple 45, the sensor 93, etc., the operation of the compressor (pump) and each valve, and the heat quantity to the heater (control means not shown) can be controlled. Is configured.

2. Method of Operating Hydrogen Storage / Supply System The hydrogen storage / supply system of the present invention is configured as described above, and the reactor has a hydrogen supplier or a hydrogen store that forms a coexisting interface between a gas phase and a liquid phase. , At least 1
It is characterized by being formed of a tubular body of a book. An example of a procedure for storing hydrogen by a hydrogen addition reaction of benzene using the hydrogen storage / supply system of the present invention and an example of a procedure for supplying hydrogen to the outside by a dehydrogenation reaction of cyclohexane will be briefly described with reference to FIG. .

When hydrogen is stored by the hydrogenation reaction of benzene, first, a high frequency current is passed through the electromagnetic induction coil 11 and the catalyst 4 is fed back by the thermocouple 45.
While adjusting the temperature of 1 to around 100 ° C., the valve 7 is opened, hydrogen is supplied to the reactor 4 from the hydrogen supply means (not shown), the valve 32 is opened, and the compressor (pump) 31 is operated. Then, a predetermined amount of benzene in the raw material storage means 2 is continuously supplied to the reaction device 4 to bring the catalyst 41 into contact with benzene and hydrogen.

At this time, gaseous cyclohexane is produced along with the hydrogenation reaction, but the produced cyclohexane is continuously supplied from the raw material supply side 42a of the tubular body 42 of the reactor 4. The liquid is discharged to the gas-liquid separation unit 5, cooled in the vapor condensing unit 51 of the gas-liquid separation unit 5, becomes liquid, and is moved to the reactant collection unit 8 and stored in the reactant collection unit 8. On the other hand, unreacted hydrogen once enters the reactant collecting means 8 and enters the hydrogen extracting section 52 of the gas-liquid separating means 5.
Although it is moved to the outside via the above, it may be configured to be connected to a hydrogen supply means to be collected and recycled.

On the other hand, when supplying hydrogen to the outside by the dehydrogenation reaction of cyclohexane, first, a high frequency current is passed through the electromagnetic induction coil 11 and the temperature of the catalyst 41 is adjusted to around 400 ° C. by feedback control by the thermocouple 45. While opening the valve 32, the compressor (pump)
31 is operated to continuously supply a predetermined amount of cyclohexane in the raw material storage means 2 to the reaction device 4 to bring the catalyst 41 into contact with cyclohexane.

At this time, gaseous benzene and hydrogen are produced along with the dehydrogenation reaction, and the produced benzene is continuously supplied from the raw material supply side 42a of the tubular body 42 of the reactor 4. Therefore, it is discharged to the gas-liquid separation means 5,
It is cooled in the vapor condensing part 51 of the gas-liquid separation means 5 to be in a liquid state, moves to the reactant collecting means 8 and is stored in the reactant collecting means 8. On the other hand, the produced hydrogen once enters the reactant recovery means 8 and moves to the outside from the hydrogen extraction section 52 of the gas-liquid separation means 5 via the pipe 91 and the sensor 93.

Although the hydrogen storage / supply system of the present invention has been described above on the assumption that it is applied to a fuel cell, it goes without saying that the hydrogen storage / supply system of the present invention is applied to a power generator other than a fuel cell. Good. For example, hydrogen may be burned to generate steam, and a turbine may be rotated to generate electricity by a generator. Further, the hydrogen storage / supply system of the present invention may be used in combination with the conventional electric power supply system such as a thermal power plant or a nuclear power plant.

3. Metal-supported catalyst The metal supported on the metal-supported catalyst used in the present invention includes nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt and iron. Examples thereof include noble metals, and these may be used alone or in combination of two or more kinds. Among them, platinum, tungsten, rhenium, molybdenum, rhodium and vanadium are particularly preferable from the viewpoint of activity, stability, handleability and the like.

The metal loading of the metal-supported catalyst is usually 0.1 to 50% by weight, preferably 0.5.
Is about 20% by weight. Further, in the case of a composite metal-based catalyst using two or more kinds of metals, the addition amount of the added metal M2 to the main metal component M1 is 0.001 to 1 in terms of M2 / M1 atomic ratio.
It is preferably 0, particularly preferably 0.01 to 5. Incidentally, M1
And M2 are the metals shown below. M1: platinum, palladium, ruthenium M2: iridium, rhenium, nickel, molybdenum,
Tungsten, ruthenium, vanadium, osmium,
Chrome, cobalt, iron

Regarding the efficiency of hydrogen storage and hydrogen supply, a carbonyl complex of the above metal, an acetylacetonate salt, a cyclopentadienyl complex, etc. are added simultaneously or sequentially to the carbon-supported platinum catalyst which is the main catalyst metal. Further, it is further improved by performing hydrogen reduction treatment after thermal decomposition.

On the other hand, as the carrier carrying the active metal,
For example, activated carbon, carbon nanotubes, molecular
Tube, porous carrier such as zeolite, silica gel,
Known carriers such as Lumina can be used, but as described above,
Using a conductor such as carbon, shape it so that eddy currents are generated.
By making it possible to directly heat the metal-supported catalyst
Is preferred. Specifically, the specific surface area is 100
0m^Two/ M^ThreeAbove, more preferably 5000 m ^Two/ M^Three
With the above, the porous metal and the electrical resistivity
Fe-like carbonaceous materials having a resistance of 100 Ω · m or less are suitable.
It

The shape of the metal-supported catalyst is not particularly limited,
The shape is appropriately selected according to the usage such as the shape of the cylindrical body to be stored.

4. Hydrogen supplier As the aromatic compound used in the present invention, benzene,
Aromatic hydrocarbon compounds such as toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, and phenanthrene, and alkyl derivatives thereof can be mentioned. Among them, benzene, toluene, xylene, naphthalene, etc. It is preferably used.

[0058]

EXAMPLES The hydrogen storage / supply system described in the embodiments of the present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Not a thing.

Example 1 An experiment was conducted using the apparatus shown in FIG. As a metal-supported catalyst, the specific surface area is about 750.
A metal porous body in which 10% by weight of platinum was supported on a nickel porous body of 0 m ² / m ³ was processed into a cylindrical shape according to the inner diameter of the cylindrical reactor. The amount of catalyst is 10g
This catalyst was stored in a quartz glass tubular reactor 4 having an inner diameter of 5 cm, and the temperature was 350 ° C. by induction heating with an output of about 1 kw.
Heat to 0.3 ml of cyclohexane as raw material
Hydrogen was generated by supplying hydrogen to the catalyst at a rate of / sec. As a result of measuring the hydrogen generation amount per minute, the hydrogen generation rate was 18 l / min.

(Example 2) The procedure of Example 1 was repeated except that the metal-supported catalyst was prepared by using felt-like carbon having an electric resistivity of about 10 Ω. An experiment was performed under the same conditions as in Example 1. As a result of measuring the hydrogen generation amount per minute, the hydrogen generation rate was 18 l / min.

(Example 3) In Example 1, 1 catalyst was used.
While heating to 00 ° C., benzene is continuously supplied at a rate of 0.3 ml / sec from the one end 42a of the reaction device 4, and
Similarly, hydrogen is supplied at a rate of 20 l / min to one end 42 of the reactor 4.
The hydrogenation reaction of benzene was carried out by continuously supplying from a. As a result, it was confirmed that 98% of the input benzene was converted to cyclohexane.

(Comparative Example 1) In Example 1, a stainless steel tubular reactor 4 having an inner diameter of 5 cm was used as a tubular reactor, a platinum catalyst was applied to the inner peripheral wall of the tubular reactor, and the output was about 1 k.
The stainless steel tubular reactor itself was heated to 3 by induction heating of w.
An experiment was conducted under the same conditions as in Example 1 except that the heating was performed directly at 50 ° C. As a result of measuring the hydrogen generation amount per minute, the hydrogen generation rate was 5 l / min.

[0063]

As described above, the hydrogen storage / supply system of the present invention is used in the range of 200 to 350, especially when hydrogen is generated.
The catalyst heated to ℃ is cooled by the low temperature liquid raw material to lower the catalyst temperature, and the endothermic reaction accompanying the dehydrogenation reaction causes the catalyst temperature to drop sharply and the reaction to stop halfway.
Since more heat energy can be supplied by following the reaction so that a part of the raw material does not remain unreacted, it is stable in the dehydrogenation reaction of the hydrogen supplier consisting of the hydrogenated derivative of the aromatic compound. There is an effect that hydrogen can be supplied efficiently and efficiently.

[Brief description of drawings]

FIG. 1 is an explanatory diagram schematically showing the configuration of a hydrogen storage / supply system of the present invention.

[Explanation of symbols]

1 Hydrogen storage and supply system 2 Raw material storage means 3 Raw material supply means 31 Compressor 32 valves 4 reactor 41 catalyst 42 Tubular body 43 heater 44 Heater storage 45 thermocouple 5 Gas-liquid separation means 51 Steam condensing section 52 Hydrogen extractor 6 valves 7 valves 8 Reactant recovery means 91 Hydrogen delivery line 92 valve 93 sensor 10 Control means 11 Electromagnetic induction coil 12 Generated gas discharging means

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 35/10 301 B01J 35/10 301J C01B 3/22 C01B 3/22 Z F17C 11/00 F17C 11/00 C H01M 8/04 H01M 8/04 J (72) Inventor Yasushi Goto 32 Wadai, Tsukuba, Ibaraki Prefecture Sekisui Chemical Co., Ltd. (72) Inventor Kazuhiro Fukada 32 Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd. In-house (72) Inventor Kazuhiro Fukaya 32, Wadai, Tsukuba, Ibaraki Sekisui Chemical Co., Ltd. F-term (reference) 4G069 AA03 AA08 BA08A BA08B BB02A BB02B BC54A BC58A BC59A BC60A BC64A BC65A BC68B BC69A BC75B CC40YEC01 EA06 EC01 EC01X EC27 4G140 AA16 AA27 AA42 DA05 DC02 DC03 DC07 5H027 AA02 BA13 MM21

Claims (13)

[Claims] 1. Storage and / or storage of hydrogen utilizing at least one of a hydrogenation reaction of a hydrogen storage body made of an aromatic compound and a dehydrogenation reaction of a hydrogen supply body made of a hydrogenated derivative of the aromatic compound. A hydrogen storage / supply system for supplying, comprising: a raw material storage means (a) for accommodating a hydrogen storage body and / or a hydrogen supply body;
Alternatively, a reactor (b) containing a metal-supported catalyst for performing dehydrogenation of the hydrogen supplier, and a raw material supply means (c) for supplying the hydrogen storage body and / or the hydrogen supply body in the raw material storage means to the reactor. A gas-liquid separation means (d) for condensing the produced gas from the reactor to separate hydrogen into a hydrogen storage body and / or a hydrogen supply body, and a reaction for recovering the separated hydrogen storage body and / or the hydrogen supply body. And a heating means (f) for heating the metal-supported catalyst. Further, the metal-supported catalyst is composed of a carrier made of a conductive material and a catalyst metal carried thereon. The hydrogen storage / supply system is characterized in that the heating means is configured to enable high frequency induction heating of the carrier. 2. The catalyst metal is at least one metal selected from the group consisting of nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron. Claim 1 characterized by the above.
The hydrogen storage / supply system described in 1. 3. The carrier has a specific surface area of 1000 m ² /
The hydrogen storage / supply system according to claim 1, wherein the hydrogen storage / supply system is a porous metal body having m ³ or more. 4. The hydrogen storage / supply system according to claim 3, wherein the metal porous body is a porous body of nickel or an alloy thereof. 5. The hydrogen storage / supply system according to claim 3, wherein the porous metal body has a cylindrical shape. 6. The carrier has an electric resistivity of 100 Ω · m.
The hydrogen storage / supply system according to claim 1, which is a felt-like carbon-based material below. 7. The reactor (b) is formed of at least one tubular body, one end of the tubular body is the raw material supply means (c), and the other end is the gas-liquid separation means (d). The hydrogen storage / supply system according to claim 1, which is in communication with the hydrogen storage / supply system. 8. A coil-shaped electromagnetic induction coil for heating the metal-supported catalyst is arranged so as to surround the main body of the tubular body of the reaction device (b), and at that time, a thermoelectric element in contact with the metal-supported catalyst is disposed. 8. The hydrogen storage / storage according to claim 7, wherein the temperature of the metal-supported catalyst is adjusted by detecting the catalyst temperature by a pair and adjusting the high frequency current to the electromagnetic induction coil.
Supply system. 9. The cylindrical porous body of the reactor (b) is filled with a cylindrical metal porous body or felt-like carbonaceous material matching the inner diameter thereof.
The hydrogen storage / supply system described in 1. 10. The hydrogen storage / supply system according to claim 7, wherein the tubular body is formed of an insulator having heat resistance, heat insulation, and non-high frequency dielectric heating. 11. The hydrogen storage / supply system according to claim 10, wherein the insulator is made of at least one inorganic material selected from the group consisting of quartz glass, alumina, and ceramics. 12. The aromatic compound is benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene,
The hydrogen storage / supply system according to claim 1, wherein the hydrogen storage / supply system is at least one compound selected from the group consisting of and an alkyl derivative thereof. 13. The hydrogenated derivative is at least one compound selected from cyclohexane, methylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, decahydronaphthalene (decalin), and alkyl derivatives thereof. The hydrogen storage / supply system according to claim 1, wherein